Water resistant polymers for personal care

ABSTRACT

Described are personal care compositions comprising a polymer comprising: (a) one or more polymer comprising, as polymerized units, (i) 75% to 35% by weight, based on the weight of said polymer, one or more (meth)acrylate monomer selected from at least one of C1-C4 (meth)acrylate, (meth)acrylic acid, styrene, or substituted styrene, and (ii) 25% to 65% by weight, based on the weight of said polymer, one or more hydrophobic monomer, including hydrophobically substituted (meth)acrylate monomers, with alkyl chain length from C8 to C22 and, (iii) optionally crosslinker, and, (b) at least one personal care active. Optionally, the polymer further includes a stage 2 polymer comprising, as polymerized units, (i) 10-99% of one or more monomer which has a Tg of more than 80° C. after polymer formation, (ii) 1-10% of one or more (meth)acrylate monomer containing acid functional group, and (iii) optionally, a crosslinker.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and is a 371 U.S.C. §371 nationalphase application of International Application No. PCT/US13/033778,filed on Mar. 26, 2013, which claims priority from U.S. ProvisionalApplication Ser. No. 61/617,240, filed Mar. 29, 2012, both of which areincorporated herein by reference in their entireties.

FIELD

The present invention relates to compositions for imparting waterresistance and aiding retention of active ingredients in personal carecompositions.

BACKGROUND

The need for compositions for imparting water resistance and aidingretention of active ingredients in personal care compositions is wellknown. Without them, personal care actives may wash off, wear off, bere-emulsified, or otherwise lose their efficacy. The problem withcurrent water resistance imparting polymers is they are typically verytacky and impart bad aesthetic feel to consumers when formulated intoleave-on formulations. For reference, aesthetics is one of the mostimportant considerations in a consumer's selection of, or at leastloyalty to, a personal care composition.

Accordingly, what is needed is a water resistance polymer whichpossesses improved aesthetic performance, as well as excellent retentionof active ingredients when water is present.

DETAILED DESCRIPTION

In one embodiment, the present invention provides personal carecompositions comprising a polymer comprising: (a)one or more polymercomprising, as polymerized units, (i) 75% to 35% by weight, based on theweight of said polymer, one or more (meth)acrylate monomer selected fromat least one of C1-C4 (meth)acrylate, (meth)acrylic acid, styrene, orsubstituted styrene, and (ii) 25% to 65% by weight, based on the weightof said polymer, one or more hydrophobic monomer, includinghydrophobically substituted (meth)acrylate monomers, with alkyl chainlength from C8 to C22 and, (iii) optionally crosslinker, and, (b) atleast one personal care active, other than a suncare active. Theresulting polymer shows superior aesthetic feel, great film formation,and has excellent retention of active ingredients in the presence ofwater.

As used herein, “(meth)acrylic” means acrylic or methacrylic;“(meth)acrylate” means acrylate or methacrylate; and “(meth)acrylamide”means acrylamide or methacrylamide. “Substituted” means having at leastone attached chemical group such as, for example, alkyl group, alkenylgroup, vinyl group, hydroxyl group, carboxylic acid group, otherfunctional groups, and combinations thereof.

Styrene and substituted Styrene monomers have one ethylenicallyunsaturated group per molecule. Examples of Styrene and substitutedStyrene monomers include 4-methylstyrene, 2-methylstyrene,3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene,4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 2-chlorostyrene,3-chlorostyrene, 4-chloro-3-methylstyrene, 4-t-butylstyrene,2,4-dichlorostyrene, 2,6-dichlorostyrene. Preferred Styrene andsubstituted Styrene monomers include styrene (Sty) and 4-methylstyrene(vinyltoluene).

Preferred (meth)acrylate monomer containing acid functional groupinclude acrylic acid, methacrylic acid, itaconic acid, crotonic acid.More preferred (meth)acrylate monomers containing acid functional groupare acrylic acid, methacrylic acid.

In one embodiment, monomer (i) is present in a range of 75% to 35% byweight. Preferred monomer (i) are (meth)acrylate monomer with alkylchain length of C4 and less, styrene, substituted styrene, Morepreferred monomer (i) are butyl acrylate, ethyl acrylate, acrylic acid,methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylicacid, styrene. Most preferred monomer (i) are butyl acrylate, methylmethacrylate, methacrylic acid, styrene. In one embodiment, whereinmonomer (ii) is one or more hydrophobic monomer, includinghydrophobically substituted (meth)acrylate monomers, with alkyl chainlength from C8 to C22. Prefered monomers (ii) are one or two monomerselected from ethylhexyl methacrylate, lauryl methacrylate, stearylmethacrylate, and cetyl-eicosyl methacrylate, behenyl methacrylate,ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, andcetyl-eicosyl acrylate, behenyl acrylate. Most preferred monomer (ii)are one or two monomer selected from ethylhexyl acrylate, laurylmethacrylate, stearyl methacrylate.

In some embodiments, the polymer further comprising a cross-linker.Crosslinkers are monomers having two or more ethylenically unsaturatedgroups, and may include, e.g., divinylaromatic compounds, di-, tri- andtetra-(meth)acrylate esters, di-, tri- and tetra-allyl ether or estercompounds and allyl (meth)acrylate. Preferred examples of such monomersinclude divinylbenzene (DVB), trimethylolpropane diallyl ether,tetraallyl pentaerythritol, triallyl pentaerythritol, diallylpentaerythritol, diallyl phthalate, diallyl maleate, triallyl cyanurate,Bisphenol A diallyl ether, allyl sucroses, methylene bisacrylamide,trimethylolpropane triacrylate, allyl methacrylate (ALMA), ethyleneglycol dimethacrylate (EGDMA), hexane-1,6-diol diacrylate (HDDA) andbutylene glycol dimethacrylate (BGDMA). Especially preferredcrosslinkers include DVB, ALMA, EGDMA, HDDA and BGDMA. Most preferredcrosslinker is ALMA. In some embodiments of the invention, the amount ofpolymerized crosslinker residue in the polymer is at least 0.01%,alternatively at least 0.02%, alternatively at least 0.05%. In someembodiments of the invention, the amount of crosslinker residue in thepolymer is no more than 0.3%, alternatively no more than 0.2%,alternatively no more than 0.15% .Polymers usefully employed accordingto the invention can be prepared by conventional emulsion, solution orsuspension polymerization. Emulsion polymerization is preferred.Monomers used to prepare the polymers are added in a sequential processor randomly to afford non-random or random polymers using a free-radicalinitiator such as peroxygen compounds or diazo compounds and,optionally, chain transfer agents. The length of the primary polymerchains is typically such that, if any crosslinks were removed, themolecular weight (Mw) would be in the range of about 50,000 to10,000,000, alternatively from 100,000 to 5,000,000, alternatively from200,000 to 2,000,000.

A free radical initiator is utilized in solution and emulsionpolymerizations. Suitable free radical initiators include hydrogenperoxide; tert-butyl hydroperoxide; sodium, potassium, lithium andammonium persulfate and the like. A reducing agent, such as a bisulfite,including an alkali metal metabisulfite, hydrosulfite, and hyposulfite;and sodium formaldehyde sulfoxylate or a reducing sugar such as ascorbicacid or isoascorbic acid, may be used in combination with the initiatorto form a redox system. Initiators usefully employed for suspensionpolymerization include oil soluble peroxides, hydroperoxides and azocompounds such as AIBN. The amount of initiator may be from 0.01% byweight to about 2% by weight of the monomer charged and in a redoxsystem, a corresponding range of 0.01% by weight to about 2% by weightof reducing agent may be used. Transition metal catalysts, such as ironand copper salts, may be used.

The polymerization temperature may be in the range of about 10° C. to120° C. in the aqueous emulsion, suspension and solutionpolymerizations. In the case of the persulfate systems, the temperatureis preferably in the range of 60° C. to 90° C. In the redox system, thetemperature is preferably in the range of 20° C. to 70° C.

For emulsion polymers, any emulsifiers or dispersing agents optionallyemployed for preparing the monomer emulsions or polymer emulsions may beanionic, cationic or non-ionic types. Also a mixture of any two or moretypes may be used. Suitable nonionic emulsifiers include, but are notlimited to, ethoxylated octylphenols, ethoxylated nonylphenols,ethoxylated fatty alcohols and the like. Suitable anionic emulsifiersinclude, but are not limited to, sodium lauryl sulfate, sodiumdodecylbenzene sulfonate, sulfated and ethoxylated derivatives ofnonylphenols, octylphenols and fatty alcohols, esterifiedsulfosuccinates and the like. Suitable cationic emulsifiers include, butare not limited to, laurylpyridinium chlorides, cetyldimethylamineacetate, (C₈-C₁₈) alkyldimethylbenzylammonium chlorides and the like.The level of emulsifier may be from about 0.1% to about 10% by weight,based on total monomer charged.

In one embodiment, monomer (i) is at least two of butyl acrylate, methylmethacrylate, methacrylic acid, or styrene.

In one embodiment, monomer (ii) is at leastone of ethylhexyl acrylate,lauryl methacrylate, stearyl methacrylate, and cetyl-eicosylmethacrylate, behenyl methacrylate, lauryl acrylate, stearyl acrylate,and cetyl-eicosyl acrylate, behenyl acrylate. In one embodiment, monomer(ii) is at least two of ethylhexyl acrylate, lauryl methacrylate,stearyl methacrylate, and cetyl-eicosyl methacrylate, behenylmethacrylate, lauryl acrylate, stearyl acrylate, and cetyl-eicosylacrylate, behenyl acrylate.

In one embodiment, the polymer is formed in a single stage.

In one embodiment, the polymer is formed in a two stage reaction. In oneembodiment, the stage 2 polymer comprises, as polymerized units, (i)10-99% of one or more monomer which has a Tg of more than 80° C. afterpolymer formation, (ii) 1-10% of one or more (meth)acrylate monomercontaining acid functional group, and (iii) optionally, a crosslinker.In one embodiment, the stage 1 and stage 2 ratio ranges from 60:40 to 99to 1.

Polymers with high glass transition temperatures (“Tg”) are typicallyused to lower the tackiness of polymer film properties. However, high Tgpolymers have the drawback that they form films that are extremely hardand brittle. Preferably, the Tg of the second stage polymer is in therange of about 50 to 200° C., alternatively from 75 to 150° C.,alternatively from 80 to 120° C.

In some embodiments of the invention, the stage 1 and stage 2 ratio ismore than 50:50, preferably more than 60:40. In some embodiments of theinvention, the stage 1 and stage 2 ratio is less than 99:1, preferably,less than 90 to 10.

The invention provides water resistance polymers, personal carecompositions and formulations including any cosmetically acceptable oilbase. A suitable oil base includes any oil or mixture of oils which areconventionally used in the personal care products. Examples includesaturated fatty esters and diesters, such as isopropyl palmitate, octylpalmitate, butyl stearate, isocetyl stearate, octadodecyl stearoylstearate, diisopropyl adipate, dioctyl sebacate, paraffin oils, paraffinwaxes, animal oils and vegetable oils such as mink oil, coconut oil,soybean oil, palm oil, corn oil, cocoa butter, sesame oil, lanolin oil,fatty alcohols such as stearyl alcohol, isostearyl alcohol, isocetylalcohol. The oils listed are merely examples are not intended to limitthe invention in any way. In general, any hydrophobic material ormixtures thereof which are toxicologically safe for human or animal usemay constitute the oil base of the present invention.

The personal care compositions and formulations containing the waterresistance polymers are of four basic compositions: oil dispersions,oil-in-water emulsions, water-in-oil emulsions and solutions from one ormore organic solvents. The oil dispersions are prepared by dispersingthe water resistance polymers in the oil base with one or more activeingredients. The water resistance polymers can be dispersed in an oilphase or are prepared as an aqueous suspension prior to preparing thefinal oil-in-water or water-in-oil emulsion. The polymers can be addedin either phase at any stage in preparing the composition orformulation. Personal care formulations are prepared by combining waterresistance polymers, an oil base, optionally including an aqueous phase,one or more active ingredients and optional additives by warming themixture with slow agitation. The oil based personal care compositionsand formulations include from 0.01 to 10% by weight of at least onewater resistance polymer based on the total weight of the formulation.The cosmetically acceptable base of the compositions and formulationsmay be solid or liquid, but the entire formulation is preferably fluidat skin temperatures for ease of application. Suitable solvents forpreparing a solution of the polymer are typically those used in the artand include alcohols such as ethyl alcohol and volatile silicones suchas cyclomethicone. Suitable additives include fragrances, fillers, dyes,colorants, preservatives, biocides, antioxidants, other such additivesconventionally used in personal care products without negativelyimpacting substantivity and combinations thereof.

The invention provides dermally applied personal care compositions andformulations including water resistance polymers dispersed in an oilbase and one or more personal care active ingredients. Suitable activeingredients include but are not limited to sunscreening actives,moisturising actives such as moisturizing agents, emollients,anti-oxidants, botanicals, skin lightening agents, cleansing actives forpersonal care, detergent actives for personal care, vitamins, folic acidderivatives, exfoliating agents, deodorising actives, fragrance actives,skin exfoliating actives, topical medicament actives for personal care,cosmetic agents for personal care, hair conditioners, facial careactives, pigments, colorants silicones, topical preparations, infrared(IR)-absorbing materials for personal care, acne medications andcombinations thereof. Cosmetic agents include for example mascaras,eyeliners, lipsticks, powders, paints, foundations and masks.

Skin care compositions and formulations of the invention may be formedusing conventional emulsion techniques and inexpensive agitationequipment. The skin care compositions and formulations thus formed arestable emulsions, the polymers effectively retaining active ingredientsat low polymer concentrations, ranging from 0.01 to 10% by polymerweight based on the total weight of the composition in the oil phase;the formulation having an oil phase viscosity of at least 10 poise undera shear stress up to 1000 dynes/cm². It is preferred that theformulation consists of an oil-in-water emulsion.

When applied to mammalian skin, these personal care compositions andformulations of the present invention form an oil film on the skinsurface. This film gives the skin a moist, glossy appearance whichprovides cosmetic elegance.

The films helps protect the skin from the drying, oxidizing effects ofthe environment. Moreover the compositions and formulations remainsubstantive for extended periods of time and prolonged exposure toaqueous environments such as water, humidity or perspiration.

Oil-in-water emulsions are generally prepared by heating the oil andwater phases, and slowly adding the water phase to the oil phase withgood agitation. Homogenization may be helpful, but it is not necessary.The addition of low levels of stabilizing ingredients in the water phasehas been shown to be helpful. Salts such as magnesium sulfate haveproven to be useful emulsion stabilizers, and they do not significantlyaffect the water resistance of the formulations. The addition of watersoluble gums such as guar derivatives, xanthan gum, and aloe vera andthickeners such as hydroxyethyl cellulose, hydroxymethyl cellulose andcarboxyvinyl polymers have been found to be helpful in stabilizing theemulsions.

The personal care compositions and formulations are usefully employed inaccordance with the present invention as creams, lotions, gels,towelettes, wipes, masks, adhesive pads, sprays delivered from solventand any conventional means used in personal care art.

The following examples illustrate specific aspects and particularembodiments of the invention which, however, are not to be construed aslimited thereby.

EXAMPLES

The following abbreviations are used in the Examples described herein:

BA=butyl acrylate

Sty=Styrene

MAA=methacrylic acid

MMA=methyl methacrylate

EHA=ethylhexyl acrylate

SMA=Stearyl methacrylate

CEMA=Cetyl-eicosyl methacrylate

ALMA=allyl methacrylate

Example 1

One stage polymers of the present invention are listed in TABLE 1:

TABLE 1 Composition Polymer 1 31 SMA/25 BA/29 Sty/15MAA Polymer 2 20BA/40EHA/38.5 MMA/1.5 MAA/0.075 ALMAA standard emulsion polymerization method is used. For example, to a2-liter round-bottom flask equipped with a overhead stirrer,thermocouple, condenser and inlets for the addition of monomer andinitiators is charged 183.5 g of deionized water, 26.6 g of 50% CAVASOL™W7 M TL (cyclodextrin from Wacker Fine Chemicals), 6.1 g of a 30%DISPONIL® FES 32 (Cognis) surfactant and 1.8 g of sodium carbonate. Theflask is stirred and heated to 92° C. A monomer emulsion is prepared bycharging 363 g of deionized water and 13.6 g of DISPONIL® FES 32surfactant to an appropriate container and set to stir. After thesurfactant is incorporated into the water, 175 g of BA, 203 g ofStyrene, 105 g of MAA and 217 g of SMA is added slowly to the stirringmixture. A cofeed catalyst solution is also prepared by charging 0.69 gof sodium persulfate and 96 g of deionized water.

At reaction temperature of 92° C., 25 g of the above prepared monomeremulsion is charged to the kettle with a 11 gram deionized water rinse,followed by an initiator solution of 2.11 g sodium persulfate and 12 gwater.

After initial polymerization and at 85° C., the monomer emulsion cofeedis begun at a rate of 6.33 g per minute for 10 minutes and 12.7 g perminute for 75 minutes. Simultaneously, the catalyst cofeed is begun at arate of 1.1 g per minute for 88 minutes. At the completion of themonomer emulsion and catalyst cofeed, the reaction mixture is chased toreduce the amount of residual monomers. The resulting Polymer 1 latexhas the following characteristics. Solids is the weight of solidmaterial left when the latex is evaporated to dryness, as a percentageof the total weight of latex. Grit is the amount of material retained inthe mesh bags. Mean particle size was measured with a BrookhavenInstruments Corp. BI-90 device. Residual Monomer amounts were measuredby head space gas chromatography.

Solids: 44.7%

Grit: <100 ppm

Mean Particle Size: 205 nm

Residual Styrene: 7 ppm

Polymer 2 is made substantially as described above, the appropriatechanges being made.

Example 2 (Comparative)

Comparative one stage polymers are listed in TABLE 2:

TABLE 2 Composition Comparative example A 31 CEMA/49 BA/18.6 MMA/1.4 MAA

The comparative polymer is made substantially as described in Example 1,the appropriate changes being made.

Example 3

Two stage polymers of the present invention are listed in TABLE 3:

TABLE 3 Composition Polymer 3 Stage 1 (85%): 31 SMA/25 BA/29 STY/15 MAAStage 2 (15%): 99 MMA/1 MAA Polymer 4 Stage 1 (80%): 31 SMA/25 BA/29STY/15 MAA Stage 2 (20%): 99 MMA/1 MAA Polymer 5 Stage 1 (70%): 31SMA/25 BA/29 STY/15 MAA Stage 2 (30%): 99 MMA/1 MAA Polymer 6 Stage 1(85%): 20 BA/40 EHA/38.5 MMA/1.5 MAA//0.075 ALMA Stage 2 (15%): 99 MMA/1MAA Polymer 7 Stage 1 (80%): 20 BA/40 EHA/38.5 MMA/1.5 MAA//0.075 ALMAStage 2 (20%): 99 MMA/1 MAA Polymer 8 Stage 1 (70%): 20 BA/40 EHA/38.5MMA/1.5 MAA//0.075 ALMA Stage 2 (30%): 99 MMA/1 MAA Polymer 9 Stage 1(80%): 20 BA/40 EHA/38.5 MMA/1.5 MAA//0.075 ALMA Stage 2 (20%): 99 MMA/1MAA//0.075 ALMA

A standard emulsion polymerization method is used. For example, forPolymer 9, 252 g of deionized water, 8 g of a 23% sodium dodecyl benzenesulfonate and 2 g of sodium carbonate are charged to a 2-literround-bottom flask equipped with a overhead stirrer, thermocouple,condenser and inlets for the addition of monomer and initiators. Theflask is stirred and heated to 92° C. A monomer emulsion (stage 1) isprepared by charging 146 g of deionized water and 5.6 g of sodiumdodecyl benzene sulfonate (23%) to an appropriate container and set tostir. After the surfactant is incorporated into the water, 90 g of BA,180 g of g of EHA, 174 g of MMA, 6.8 g of MAA, and 0.34 g of ALMA isadded slowly to the stirring mixture. A cofeed catalyst solution is alsoprepared by charging 0.86 g of sodium persulfate and 50 g of deionizedwater.

At reaction temperature of 88° C., 19 g of the above prepared monomeremulsion is charged to the kettle with 5 g of deionized water rinse,followed by an initiator solution of 1.9 g sodium persulfate and 15 gwater. After initial polymerization and at 85 ° C., the stage 1 monomeremulsion cofeed is begun at a rate of 4.72 g per minute for 15 minutesand 10.1 g per minute for 83 minutes. Simultaneously the stage 1catalyst cofeed is begun at a rate of 0.61 g per minute for 88 minutes.At the completion of the monomer emulsion and catalyst cofeed, thereaction mixture is held for 10 minutes.

During the feed of stage 1, stage 2 monomer emulsion and catalyst areprepared. Stage 2 monomer emulsion is prepared by charging 52 g ofdeionized water and 2 g of sodium dodecyl benzene sulfonate (23%) to anappropriate container and set to stir. After the surfactant isincorporated into the water, 112 g of MMA, 1.1 g of g of MAA, and 0.09 gof ALMA is added slowly to the stirring mixture. A stage 2 cofeedcatalyst solution is also prepared by charging 0.12 g of sodiumpersulfate and 14 g of deionized water. Upon the completion of stage 1hold, the stage 2 monomer emulsion cofeed is begun at a rate of 6.55 gper minute for 29 minutes.

At the completion of the stage 2 monomer emulsion and catalyst cofeed,the reaction mixture is chased to reduce the amount of residualmonomers. The resulting latex has the following characteristics.

Solids: 43.5%

Grit: <100 ppm

Mean Particle Size: 103 nm

Residual EHA: 29 ppm

Polymers 3-8 are made substantially as described above, the appropriatechanges being made.

Example 4

Personal care formulations of the present invention are prepared withthe components listed in TABLE 4 in weight percent, and Comparativeformulations lack the inventive polymer(s).

TABLE 4 Comparative Foundation Foundation Phase Component 1 A ADeionized Water 78.0 80.0 CARBOPOL ULTREZ 10 Carbomer 0.1 0.1 Glycerin2.0 2.0 B PROCOL CS-20-D Cetearyl Alcohol 3.0 3.0 (and) Ceteareth-20Glyceryl Stearate 1.0 1.0 Petrolatum 3.0 3.0 Isopropyl Palmitate 4.0 4.0DC 200 Dimethicone 8.0 8.0 CHROMA-LITE DARK BLUE CL 0.25 0.25 4501Pigment (mica, bismuth oxychloride, ferric ammonium ferrocyanide)Triethanolamine 99% q.s. to q.s. to pH <7 pH <7 C At least one ofPolymers 1-9 2 — D Citric acid q.s. to q.s. to pH 5.5~7 pH 5.5~7Preservative (DMDM Hydantoin) 0.3 0.3The cosmetic formulations are prepared by adding all phase A ingredientsinto a container and heating to 75° C. All phase B ingredients are addedto another container and heated to 75° C. to form an oil phase. Thenphases A and B are combined at 75° C., pH adjusted to less than 7, andthe Phase C (when present) is added. The formulation is cooled to 45° C.and phase D ingredients are added, then the formulation allowed to coolto ambient temperature.

Example 5

Examples of Foundation 1 lotion and Comparative Foundation A lotion aredrawn into several samples of films with 6 MILS drawn-down on a LenetaForm 2A-Opacity Card and allowed to dry overnight.

Five trained panelists each rub a film with a folded piece of gauze, andthen rate on a scale of 1-5 how easy (1) or hard (5) it is to rub thelotion off the substrate. Results will show that Foundation 1 film isapproximately twice as hard to rub-off as Comparative Foundation A, suchrub-off resistance being beneficial.

To determine water resistance, a film is subjected to 0.06 Gallon/min at34° C., 15 cm distance to the card, with a 45° angle flow over thesample for 30 seconds. Results will show that Comparative Foundation Awashes off readily, whereas the Foundation 1 film exhibits excellentwater resistance.

1. A personal care composition comprising a polymer comprising: (a) oneor more polymer comprising, as polymerized units, (i) 75% to 35% byweight, based on the weight of said polymer, one or more (meth)acrylatemonomer selected from at least one of C1-C4 (meth)acrylate,(meth)acrylic acid, styrene, or substituted styrene, and (ii) 25% to 65%by weight, based on the weight of said polymer, one or more hydrophobicmonomer, including hydrophobically substituted (meth)acrylate monomers,with alkyl chain length from C8 to C22 and, (iii) optionallycrosslinker, and, (b) at least one personal care active other than asuncare active.
 2. The personal care composition of claim 1, whereinmonomer (i) is at least two of butyl acrylate, methyl methacrylate,methacrylic acid, or styrene.
 3. The personal care composition of claim1, wherein monomer (ii) is at leastone of ethylhexyl acrylate, laurylmethacrylate, stearyl methacrylate, and cetyl-eicosyl methacrylate,behenyl methacrylate, lauryl acrylate, stearyl acrylate, andcetyl-eicosyl acrylate, behenyl acrylate.
 4. The personal carecomposition of claim 1, wherein monomer (ii) is at least two ofethylhexyl acrylate, lauryl methacrylate, stearyl methacrylate, andcetyl-eicosyl methacrylate, behenyl methacrylate, lauryl acrylate,stearyl acrylate, and cetyl-eicosyl acrylate, behenyl acrylate.
 5. Thepersonal care composition of claim 1, wherein the personal care activeis at least one of moisturising actives such as moisturizing agents,emollients, anti-oxidants, botanicals, skin lightening agents, cleansingactives for personal care, detergent actives for personal care,vitamins, folic acid derivatives, exfoliating agents, deodorisingactives, fragrance actives, skin exfoliating actives, topical medicamentactives for personal care, cosmetic agents for personal care, hairconditioners, facial care actives, pigments, colorants silicones,topical preparations, infrared (IR)-absorbing materials for personalcare, acne medications and combinations thereof.
 6. The personal carecomposition of claim 1, wherein the polymer is formed in a single stage.7. The personal care composition of claim 6, wherein the polymer is: 31SMA/25 BA/29 Sty/15MAA; or 20 BA/40EHA/38.5 MMA/1.5 MAA/0.075 ALMA 8.The personal care composition of claim 1, wherein the polymer is formedin a two stage reaction.
 9. The personal care composition of claim 8,wherein the stage 2 polymer comprises, as polymerized units, (i) 10-99%of one or more monomer which has a Tg of more than 80° C. after polymerformation, (ii) 1-10% of one or more (meth)acrylate monomer containingacid functional group, and (iii) optionally, a crosslinker.
 10. Thepersonal care composition of claim 8, wherein the stage 1 and stage 2ratio ranges from 60:40 to 99 to
 1. 11. (canceled)